Esters of alpha-ethacrylic acid



Patented z? ps'r 'rEs- PATE 2,388,844 Es'rEns F ALPHA-ETHACRYLIC Acm Rudolph Leonard Hasche and William P. Utermohlen, Jr., Kingsport, Temp, assignors to Eastman Kodak Company, Rochester, N. Y., a

corporation of New Jersey r FFICE No Drawing. Application January 7, 1943, Serial No. 471,608

4 Claims. (Cl. 260-486) This invention relates to esters of a-ethacrylic an azeotrope leaving the ester. The water layer v acid and to a process for preparingthem. may be removed from the condensed distillate, Esters of ir-methacrylic acid are well known. and the alcohol layer returned to the reaction They have been prepared by dehydrating esters mixture, preferably in a continuous fashion. At of a-hydroxy acids and by dehydrohalogenating 5 least about 2 molecular proportions (e. g. from esters of a-halogeno acids. The meth l ester of bout 2 o a ut '4 lecula propo t o o a a-methacrylic acid can also be prepared by direct cohol .for each molecular D PQ I of field are esterification of a-methacrylic acid with methyl advantageously employed. This embodiment is alcohol. On the other hand; the preparation of sp y useful f th preparation of -1 1 the higher esters of a-methac'rylic acid by direct l0 y butyl. -P y a yl a a y ill-ethaesterification with higher alcohols has' been ry fraught with difiiculties owing, amon other According Still another embodiment P 9 things, to polymerization. For this reason, a invention, we heat c-ethacrylic acid with an number of the higher esters of a-methacrylic acid equivalent a o t of an alcohol in the presence have been prepared from the methyl ester by an 15 of an acid esterification catalyst and a water 1mester interchange process wherein the methyl esmiscible Organic liquid n ng agent, h ter is treated with ahigher alcohol. benzene, toluene, y for p The We have now found th t nk esters of water immiscible liquid and water formed during d-methacrylic acid, esters of a-ethacrylic acid of esterifioation are r ed as a a r pe leavin all kinds can be prepared by direct esterification e e The Water layer y n s case 9,150 of a-ethacrylic acid with an alcohol. By this be removed from the condensed distillate, and the method, we have be n abl t provide a number layer of organic entrainer liquid returned to the of esters of a-ethacrylic acid which were unknown reaction tu preferably in a continuous prior to our invention. Only the methyl and fashion- This method is especially useful for the ethyl esters of a-ethacrylic acid were known here- Preparation of eSlJBrS 0f a-ethaclylic ac d I101? tofore and these wer prepared by dehydratio of mentioned above, particularly those formed from methyl and ethyl a-hydroxy isovaleratea alcohols of high boiling point (above 140 C.)

It is accordingly, an object of our invention to The l ng examples Will ve o i t a provide new esters of a-ethacrylic acid. A furr new esters nd t e ann r of o ta nin th ther object is to provide a process for preparing Same! such esters. Other objects will become apparent Emmple lrrAllI/l ll hereinafter. 100 g. (1 mol.) of a-ethacrylic acid, 120 g. (2.08

' In accordance Vmh the mventlon, We prepared moi.) of allyl alcohol and 1 cc. of concentrated esters of e-ethecrvlio acid by estelification 0f the sulfuric acid were mixed together. The mixture acid with an alcohol- The esterification is was refluxed under a reflux condenser for 16 vantageously eiTected in the presence of an esterihours At the end of this time the mixture was fication catalyst, such as an acid esterification distilled at atmospheric pressure until only unre catalyst, .eg. Sulfuric acid. a. Sulfonic acid, etc. I acted ..ethacrylic acid and cataly t remained in According to one embodiment of our inven o the still. The ester layer of the distillate was we heat .u-ethacrylic acid with an excess of an 40 washed with a small amount of a 20 percent alcohol, in the presence of an acid esterification aqueous solution of sodium bisulflte, in order to' y t At l about 2 m l r P portions remove color, then with a slight excess of a dilute ef about 2 t a ut 4 m ular pr p rsolution of sodium bicarbonate, and finally with trons) of alcohol for each molecular propo water until the liquid being washed was neutral. tlon of acid ar a vantage usly employed. The The washed liquid was then distilled-in vacuo and water which is formed during the esteriflcation in 96 g. (69 percent yield) of water-white, clear allyl this embodiment is retained in the reaction mixn-ethacrylate boiling at 79 to 80 C. at mm. of Ei Thls 81111 is p lly useful for mercury pressure were obtained. g gigsg gg of n propyl' lsopmpy and anyl 50 Example 2.--Isoamyl a ethacrulate According to a further embodiment of our-in- 200 g. (2 m0l.) of a-ethacrylic acid, 230 8. (2.6 vention, we heat a-ethacrylic acid with an excess moi.) of isoamyl alcohol and 1 g. p-toluene sulof an alcohol in thepresenceof anacid esterifltonic acid were mixed-together. The mixture was cation catalyst. The excess alcohol and water refluxed under a reflux condenser in a fashion formed during the esterificationareremovedras such as to permit the distillation and removal 0t a 20 percent aqueous solution of sodium bisulflte in order to remove color, then with a dilute sodium biscarbonate solution, and finally with water fact that water no longer separated in the disuntil the liquid being washed was neutral. The

washed liquid was then distilled in vacuo. 278 g. (81 percent yield) of isoamyl a-ethacrylate were obtained as a water-white, clear liquid with a pleasant odor and boiling at 90 to 91 C. at 20 mm. of mercury pressure.

Example 3-.2-ethyl-n-primary butyl' a-ethacrz/late 125 g. (1.25 mol.) of a-ethacrylic acid, 135 g. (1.3 mol.) of 2-ethyl-n-primary butanol, 60 cc. of toluene and 1 g. of p-toluene sulfonic acid were mixed together. The mixture was refluxed under a reflux condenser in a fashion such as to permit distillation and removal of water entrained by the toluene, the apparatus being equipped with a water trap, and to permit the continuous return of the organic liquid layer of the distillate to'the reaction mixture. Refiuxing was continued until no more water separated in the distillate. At the end of this time the reaction mixture was cooled and was washed with a 20 percent aqueous solution of sodium bisulflte in order to remove color, then with a slight excess of a dilute aqueous solution of sodium bicarbonate, and finally with water until the liquid being washed was neutral. The washed liquid was then distilled in vacuo. After the removal of water and toluene in the forerun, 204 g. (89 percent yield) of Z-ethyl-n-primary butyl a-ethacrylate were obtained as a clear, water-white liquid boiling at 77 C. at 1.5 mm. of mercury pressure.

Example 4.Ethylene glycol cli-a-ethacrylate 62 g. (1 mol'.) of ethylene glycol, 200 g. (2 mol.) of a-ethacrylic acid and 1 ml. of concentrated sulfuric acid were mixed together. Toluene (75 ml.) was added to the mixture as an entraining agent for water formed during the esteriflcation. The mixture was heated so that the entraining agent and water distilled off. theentraining agent being continuously returned to the reaction mixture. Heating was continued until water no longer separated in the distillate. The reaction mixture was cooled, washed successively with dilute sodium bisuifite and sodium bicarbonate solutions, and finally washed with water until neu-,

tral. The organic liquid layer was separated from the aqueous layer and then distilledin vacuo. A -60 percent yield of ethylene glycol di-a-ethacrylate was obtained as a water-white limpid liquid with a pleasant odor which boiled at 105' C. at 1.5 mm; of mercury pressure. Example i.-Diethylene glycol di-a-et-hacryllate 106. g. (1 mol.) of diethylene glycol and 200 s. (2 mol.) of a-ethacrylic acid were mixed with a 0,5 m1. of sulfuric acid and m. of toluene. As

in the preceding example, the mixture was heat ed until no more water separated in the distillate. The ester mixture wascooled, washed successively with dilute sodium bisulfite and sodium bicarcol di'-u-ethacrylate, boiling at 130" c. at 1.5 mm.

of mercury pressure, was obtained. Example 6.T1'iethylene glycol di-a-ethacmlare 150 g. (1'mol.) of triethylene glycol and 200 g. of a-ethacrylic acid were esterified as in the preceding example using ml. of toluene as the water entraining agent and about 2 g. of 15 mmene sulfonic acid as catalyst. After the reaction had proceeded to completion as evidenced by the Example 7.-Glycerol tri-c-ethacrylate 92 g. of glycerol and300 g. of 'a-ethacrylic acid were esterifled under reflux with 120 ml, of toluene as the water entraining agent and with 1 ml. of concentrated sulfuric acid as catalyst. After esterification was complete, as indicated by the fact that water no longer separated in, the distillate, the reaction mixture was cooled, and washed with dilute sodium bisulflte solution. The ester was extracted with diethyl ether, and

the ether solution was washed with a slight excess ofdilute sodium bicarbonate solution, and then with water until neutral. The ether was removed atnormal pressure, and the residue was fractionated in vacuo. The glycerol tri-a-ethaci'ylate was obtained as a slightly viscous liquid with a pleasant odor, boiling at 113C. at 0.15 mm. of mercury pressure.

Example 8.-Propyle1 e glycol di-a-ethacrylate g. (1.05mol.) oi propylene glycol, 200 g. (2 mol.) of a-ethacrylic acid, and 75 ml. of toluene were'heated'under reflux with l g. of p-toiuene sulfonic acid as catalyst. The water produced in thereaction was withdrawn as the toluene azeotrope, returning the toluene layer of the distillate to the reaction mixture. Reaction was continued until the water no longer separated in the distillate. The reaction mixture was then worked up as described in Examples 4, 5 and 6. The ester layer was then distilled in vacuo'and obtained as a colorless liquid boiling at 122 C. at 1.5, mm. of mercury pressure.

Eiample 9.B-(n-primary butoary) ethyl-aethacrylate 240 g. (2.03 mol.) of p-n-primary butoxy ethanol (butyl cellosolve), 200g. of a-ethacrylic acid, 75 ml. of toluene, and 1 ml. of concentrated sulfuric acid as catalyst were heated together under reflux, as in earlier. examples, until water no longer separated in the distillate. The organic liquid layer or the distillate was continuously returned to the reaction mixture. The reactionmixture was then worked up by a procedure similar to that described in Example 3 above. The washed neutral ester-toluene mixture was fractionated .in vacuo'; the ester was obtained as a colorless liquid boiling at 91 C.

at 1.5 mm. of mercury pressure,- in 84 percent yield.

fi-benzyloxy ethyl a-ethacrylate and the various carbitol a-ethacrylates (esters of a-ethacrylic acid with diethylene glycol mono-allq/l ethers) .can be prepared in a similar fashion. So, also, can p-methoxy ethyl and p-ethoxy-eth- The ester layer waspearance of the second liquid phase in the distillate.

The following table contains the boiling points of a representative group of esters of a-ethacrylic acid which we have prepared by our new process.

Alcohol em 1 ed B P" mm o? p 07 ester 2-ethyl firil l'l rybllty Methyl isobutyl Ally] Ethyl Carbitol n-Primarybutyl Carbito1" fl-Benzoxyethyl nz 2-nitro-lbutanol B-Diethylaminoeth Ethylene glycoL--- Diethylene gl 001..-- Triethylene g ycol. GlyoeroL'. Propylene glycol..-

We have found that the majority of the esters of monohydrlc alcohols and a-ethacrylic acid do not undergo homopolymerization to give solid polymers. In this respect these esters difier very markedly from the corresponding esters of amethacrylic acid. However, we have also found that allyl a-ethacrylate differs from the other esters of monohydric alcohols in that it undermu-macaque- Example 11 .Polymer of ethylene glycol di-aethacrylate 100 g. of ethylene glycol di-a-ethacrylat were mixed with 1.0 g. of benzoyl peroxide. The mixture was heated at 60 C. for about 48 hours. A hard, sparkling, transparent, water-white solid was obtained which was free from bubbles and other imperfections.

Example 12.-Polymer. of diethylene glyco .di-a-ethacrylate 100 g. of diethylene glycol di-a-ethacrylate were mixed with 1.0 g. of benzoyl peroxide. The mixture was heated at 60 C. for about 72 hours. As in the preceding case, the polymer was a crystal clear, water-white product free from bubbles. The polymer had a density of 1.2.

Example 13.Polymer of triethylene glycol di-u-ethacrylate v 100 gfof triethylene glycol di-a-ethacrylate were mixed with 0.5 g. of benzoyl peroxide and goes homopolymerization when heated in the I presence of a polymerization catalyst such as an organic peroxide, e. g. benzoyl peroxide, to give a clear, hard, bubble-free infusible resin. This is surprising not Only because the other esters of a-ethacrylic acid and monohydric alcohols do not polymerize, but also because a very large part of the known allyl compounds fail to undergo homopolymerization to yield resinous homopolymers.

The esters of a-ethacrylic acid and polyhydric alcohols are quite different from the esters of monohydric alcohols in that, the esters of the polyhydric alcohols undergo homopolymeri'zation to yield clear, hard, bubble-free infusible resinous polymers. 8

The following examples will serve to illustrate the resinous homopolymers that can be prepared from some of our new esters:

Example Ill-Polymer of allyl a-ethacrylate 100 g. of allyl' u-ethacrylate were mixed with 0.5 g. of benzoyl peroxide. Th mixture wa heated at 60 C. for 14 days. A hard, water-white the mixture heated at 60? C, for 96 hours. The resulting polymer possessed a sparkling transparency, was water-white and 'free from bubbles.

Example 14.--Polymer of glycerol tri-a ethacrylate Example 15.Polymer of propylene glycol di-aethacrylate 100 g. of propylene glycol di-u-ethacrylate were mixed with 1 g. of benzoyl peroxide. The mixture was heated at 60 C. for about 72 hours, the completion of polymerization being evidenced by freedom from all odor. A clear, transparent, waterwhite solid polymer was obtained, having a density of approximately 1.2.

The estersof a-ethacrylic acid which do not undergo polymerization are useful in certain cases for the preparation of copolymers with other vinyl compounds. For example, many of the esters of -ethacrylic acid which do not undergo homopolymerization can be co-polymerized with a-ethacrylic acid to give resinous products with desirable properties. As an illustration, when aethacrylic acid and B-methoxyethyl a-ethacrylate Example 16.COPolymer of e-ethozyethyl-aethacrylate and -ethacrylic acid Equal parts by weight of beta-ethoxyethylalpha-ethacrylat and alpha-ethacrylic acid were mixed, 1% by weight of benzoyl peroxide was added, and the whole was stored at 60 C. for hours. The entire mixture had copolymerized to give aslightl yellow, clear, hard solid. The polymeric material was molded to give a clear, hard,- somewhat brittle plate. The same mono- The other 3-" 4- t I -2,sss,s44

e 1. An alkoxyaikyl e-ethaorylate.

2. p-methoxyethyl a-ethacrylate. 3. p-ethoxyethyl-a-ethacrylate.

4. p-(n-primary but Xm-ethyI-a-ethacryIate.

RUDOLPH LEONARD HASCHE. WILLIAM P. UTERMOHIEN, JR. 

